U.S. Pat. No. 4,676,887 discloses refining of petroleum hydrocarbons to product motor fuels and other products. The process described in U.S. Pat. No. 4,676,887 operates by hydrocracking a highly aromatic feed which is produced by catalytic cracking of a suitable petroleum fraction, usually a vacuum gas oil. During the catalytic cracking the dealkylation processes characteristic of the catalytic cracking process remove alkyl groups from the polyaromatic materials in the feed to produce the gasoline as the main product together with various other higher boiling fractions. A highly aromatic distillate fraction formed in the cracking and boiling from about 400.degree. F. to 750.degree. F. (about 205.degree. to 400.degree. C.), generally referred to as cycle oil, forms a preferred feed for the subsequent hydrocracking step which converts the bicyclic aromatics (naphthalenes) in the oil under relatively mild conditions to monocyclic aromatics in the gasoline boiling range. In this way, the cycle oil from the cracking process is converted to a gasoline range product, which, being highly aromatic, has a high octane value and can therefore be incorporated directly into the refinery gasoline pool without the need for subsequent reforming. The process uses relatively mild conditions e.g., hydrogen pressure under 1000 psig, (about 7000 kPa abs) and moderate conversion coupled with an acceptably low catalyst aging rate so that long cycle durations may be obtained. Reference is made to U.S. Pat. No. 4,676,887 for a detailed description of the process.
As mentioned above, a cycle oil from the catalytic cracking step is used as the feed to the hydrocracking step and usually a light cycle oil boiling approximately in the range of 400.degree. to 700.degree. F. (about 205.degree. to 400.degree. C.) is suitable. However, if a light cut-light cycle oil with an end point of not more than about 650.degree. F. (345.degree. C.), preferably not more than about 600.degree. C. (about 315.degree. C.) is used, it is possible to operate at higher conversion levels without a concomitant increase in hydrogen pressure while still maintaining an acceptable aging rate in the catalyst. In addition, the octane rating of the hydrocracked gasoline is higher. Thus, by suitable choice of the hydrocracker feed, an extended range of operating conditions may be utilized while improving product quality. The use of the light cut light, cycle oil in this process is disclosed in U.S. Pat. No. 4,738,766, to which reference is made for a detailed disclosure of the process.
Because the hydrocracking is operated under relatively low hydrogen pressure, conversion is maintained at a relatively moderate level in order to maintain catalyst aging at an acceptable rate. One consequence of this is that the effluent from the hydrocracker contains significant quantities of unconverted material, i.e. products boiling above the gasoline boiling range. The hydrocracking step has effected a removal of a significant amount of the heteroatom containing impurities in the cycle oil feed and this is reflected by relatively low sulfur and nitrogen contents in the gasoline conversion product as well as in the higher boiling fractions. In addition, some of the higher boiling fractions have undergone hydrogenation to form more readily crackable components, and for this reason a useful aspect of the process is in the recycle of the unconverted hydrocracker bottoms to the catalytic cracking unit. A process of this type is disclosed in U.S. Pat. No. 4,789,457 to which reference is made for a detailed description of the process.
We have now found that solid acid catalysts comprising a Group IVB metal oxide modified with an oxyanion of a Group VIB metal may be used as hydrocracking catalysts for cycle oil and other highly aromatic feeds. It is an object of the present invention to provide a hydrocracking process using a catalyst which results in significant boiling range conversion of heavier cycle oil components to lighter liquids and with low production of C.sub.1 -C.sub.4 gases.